Evidence for the HOOO- anion in the ozonation of 1,3-dioxolanes: hemiortho esters as the primary products

Božo Plesničar; Janez Cerkovnik; Tell Tuttle; Elfi Kraka; Dieter Cremer

doi:10.1021/ja0276319

Evidence for the HOOO^- anion in the ozonation of 1,3-dioxolanes: hemiortho esters as the primary products

Božo Plesničar^*, Janez Cerkovnik, Tell Tuttle, Elfi Kraka, Dieter Cremer

^*Corresponding author for this work

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

43 Citations (Scopus)

Abstract

Low-temperature ozonation (-78 °C) of 2-methyl-1,3-dioxolane (1a) in acetone-d₆, methyl acetate, and tert-butyl methyl ether produced both the corresponding acetal hydrotrioxide (3a, ROOOH) and the hemiortho ester (2a, ROH) in molar ratio 1:5. Both intermediates were fully characterized by ¹H, ¹³C, and ¹⁷O NMR spectroscopy, and they both decomposed to the corresponding hydroxy ester at higher temperatures. The mechanism involving the HOOO^- anion formed by the abstraction of the hydride ion by ozone to form an ion pair, R⁺ -OOOH, with its subsequent collapse to either the corresponding hemiortho ester (ROH) or the acetal hydrotrioxide (ROOOH) was proposed. This mechanism is supported by the PISA/B3LYP/6-311++G(3df,3pd) calculations.

Original language	English
Pages (from-to)	11260-11261
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	124
Issue number	38
Early online date	28 Aug 2002
DOIs	https://doi.org/10.1021/ja0276319
Publication status	Published - 25 Sept 2002

Keywords

low-temperature ozonation
decomposition
organic materials

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10.1021/ja0276319

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title = "Evidence for the HOOO- anion in the ozonation of 1,3-dioxolanes: hemiortho esters as the primary products",

abstract = "Low-temperature ozonation (-78 °C) of 2-methyl-1,3-dioxolane (1a) in acetone-d6, methyl acetate, and tert-butyl methyl ether produced both the corresponding acetal hydrotrioxide (3a, ROOOH) and the hemiortho ester (2a, ROH) in molar ratio 1:5. Both intermediates were fully characterized by 1H, 13C, and 17O NMR spectroscopy, and they both decomposed to the corresponding hydroxy ester at higher temperatures. The mechanism involving the HOOO- anion formed by the abstraction of the hydride ion by ozone to form an ion pair, R+ -OOOH, with its subsequent collapse to either the corresponding hemiortho ester (ROH) or the acetal hydrotrioxide (ROOOH) was proposed. This mechanism is supported by the PISA/B3LYP/6-311++G(3df,3pd) calculations.",

keywords = "low-temperature ozonation, decomposition, organic materials",

author = "Bo{\v z}o Plesni{\v c}ar and Janez Cerkovnik and Tell Tuttle and Elfi Kraka and Dieter Cremer",

year = "2002",

month = sep,

day = "25",

doi = "10.1021/ja0276319",

language = "English",

volume = "124",

pages = "11260--11261",

journal = "Journal of the American Chemical Society ",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Evidence for the HOOO- anion in the ozonation of 1,3-dioxolanes

T2 - hemiortho esters as the primary products

AU - Plesničar, Božo

AU - Cerkovnik, Janez

AU - Tuttle, Tell

AU - Kraka, Elfi

AU - Cremer, Dieter

PY - 2002/9/25

Y1 - 2002/9/25

N2 - Low-temperature ozonation (-78 °C) of 2-methyl-1,3-dioxolane (1a) in acetone-d6, methyl acetate, and tert-butyl methyl ether produced both the corresponding acetal hydrotrioxide (3a, ROOOH) and the hemiortho ester (2a, ROH) in molar ratio 1:5. Both intermediates were fully characterized by 1H, 13C, and 17O NMR spectroscopy, and they both decomposed to the corresponding hydroxy ester at higher temperatures. The mechanism involving the HOOO- anion formed by the abstraction of the hydride ion by ozone to form an ion pair, R+ -OOOH, with its subsequent collapse to either the corresponding hemiortho ester (ROH) or the acetal hydrotrioxide (ROOOH) was proposed. This mechanism is supported by the PISA/B3LYP/6-311++G(3df,3pd) calculations.

AB - Low-temperature ozonation (-78 °C) of 2-methyl-1,3-dioxolane (1a) in acetone-d6, methyl acetate, and tert-butyl methyl ether produced both the corresponding acetal hydrotrioxide (3a, ROOOH) and the hemiortho ester (2a, ROH) in molar ratio 1:5. Both intermediates were fully characterized by 1H, 13C, and 17O NMR spectroscopy, and they both decomposed to the corresponding hydroxy ester at higher temperatures. The mechanism involving the HOOO- anion formed by the abstraction of the hydride ion by ozone to form an ion pair, R+ -OOOH, with its subsequent collapse to either the corresponding hemiortho ester (ROH) or the acetal hydrotrioxide (ROOOH) was proposed. This mechanism is supported by the PISA/B3LYP/6-311++G(3df,3pd) calculations.

KW - low-temperature ozonation

KW - decomposition

KW - organic materials

UR - https://www.scopus.com/pages/publications/84961980727

UR - https://pubs.acs.org/journal/jacsat

U2 - 10.1021/ja0276319

DO - 10.1021/ja0276319

M3 - Article

AN - SCOPUS:84961980727

SN - 0002-7863

VL - 124

SP - 11260

EP - 11261

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 38

ER -

Evidence for the HOOO^- anion in the ozonation of 1,3-dioxolanes: hemiortho esters as the primary products

Abstract

Keywords

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